Production of alcohols



Reissued Oct. 14, 1941 18 Claims.

The present invention relates to the production of alcohols.

I have found that aliphatic, cycloaliphatic, aliphatic aromatic or aromatic hydrocarbons and their homologues, boiling above C. at atmospheric pressure, are converted into alcohols in a simple and advantageous manner by treating them in the presence of a Frledel-Crafts condensing agent with alkylene oxides, if desired at a pressure above atmospheric pressure.

Suitable hydracarbons are for example ,pentane, hexane, heptane, do decene, octadecene and the like, cyclohexane, hexahydrotoluene, benzene, toluene, naphthalene and the like. Mixtures of hydrocarbons which occur naturally or which are formed industrially may also be employed, as for example those which are present in petroleum fractions, benzlnes, paraifins, middle oils, brown coal tar oils and products of the destructive hydrogenation of coals, tars and the like.

For the treatment of the said initialv mate-' rials, alkylene oxides, such as ethylene oxide, 1.2- or 1.3-propy1ene oxides, normal butylene oxides, isobutylene oxide, trimethylethylene oxide, glycide and the like may be employed. Th Friedel- Crafts condensing agents are for example anhydrous aluminum halides, such a as aluminum chloride, bromide or iodide, boron fluoride, anhydrous iron chloride and like acid reacting halides of solid elements melting above 300 C. as are usually employed in Frieda-Crafts reactions.

Generally speaking the reaction takes place even at room temperatures by bringing the reaction components together or even at between 0. below and above zero. It is frequently advantageous, however, to work at higher temperatures, say up to about 100 0., in order to accelerate and complete the reaction. When readily volatile compounds are employed, such as ethylene oxide or butane, it is preferable to carry out the reaction in closed vessels, so that a pressure above atmospheric pressure may be generated. Organic diluents which are inert under the conditions of working may also be employed as for example carbon disulphide or carbon tetra- "chloride, especially on worlclng with solid initial materials which may be liquefied by the addition of the said solvents. The working up of the reaction mixture, which is usually obtained in the form of a viscous mass, is carried out by decomposition with ice and water, separation of the alcohols from unchanged initial material and fractional distillation.

UNlTED STATES PATENT OFFICE rnonuc'rroN or aLconoLs Heinrich Hopfl', Ludwigshafen-on-the-Rhine, Germany, assignor, by mesne assignments, to Winthrop Chemical Company, Inc., New York, N. Y., a corporation of New. York No Drawing. Original No. 2,029,618, dated February 4, 1936. Serial No; 536,670, May 11, 1931. Application for reissue June 8, 1940, Serial No. 339,582. In Germany May 23, 1930 the nature of this invention, but the invention is mosphere The temperatures of working must not considformedmay react with remainders-of th initial materials with the formation of hydrocarbons by splitting on water. a

The following examples will further illustrate not restricted to these examples. The parts are by weight.

Example 1 .phenyl urethane is 79 C.

If the ethylene oxide be led in not at ordinary temperature but at from about to C. in addition to phenylethyl alcohol a considerable amount of dibenzyl is formed from the phenylethyl alcohol first formed by further condensation with benzene with the splitting off of water.

Example 2 250 parts of anhydrous aluminum bromide are added to 500 parts or normal pentane and ethylene oxide is led into the mixture at room temperature while stirring vigorouslyuntil no further absorption of ethylene oxide takes place. The reaction product. is worked up as described in Example 1 and yields 25 parts of an oil which boilsmainly between and C; and contains considerable amounts of normal heptyl alcohol.

Other hydrocarbons, as for example, hexane, heptane, and th like or mixtures of hydrocarbons, such as benzines, varieties of kerosene and the like may be employed instead of normal pentane. Other alkylene oxides, such as propylene oxide, butylene oxide and the like react in the same manner.

Example 3 150 parts of anhydrous aluminum chloride are added to 500 parts of an American kerosene in an autoclave and the whole treated with ethylene oxide at room temperature and at about 0.5 at- (superatmospheric pressure) there is no further decrease in pressure. The

until reaction product consists of a brownish colored 7 very viscous lower layer and a colorless upper layer. The latter contains only unchanged petroleum and is poured oil. treated with ice and th resulting 32 parts of oily product are separated from water. It boils between 150 and 200 C. at 12 millimeters meroury gauge and consists of higher alcohols.

Example 4 500 parts of cyclohexane are mixed. while cooling, with 132 parts of anhydrous aluminum chloride and 50 parts of ethylene oxide are added,

while cooling and stirring, the aluminum chloride being gradually converted into a viscous pasty mass. unaltered cyclohexane is drawn oil and the tough residue is decomposed by adding a mixture of ice and water. After adding 100 parts of'concentrated hydrochloric acid, the reaction product is distilled with steam. After extraction of the distillate with ethyl ether, the extract'furnishes '10 parts of an oil, boiling mainly at from 95 to 105 C. at 13 millimeters of mercury and consisting mainly of hydroxyethyl cyclohexane.

Example 128 parts of naphthalene dissolved in 400 parts of carbon disulphide are incorporated with 132 parts of anhydrous aluminum chloride, where- 0 upon about 50 parts of ethylene oxide are gradually added while stirring and cooling. 0n working up as described in the foregoing example; 60 parts of an oil are obtained which boils from 145' to 150 C. at 2 millimeters of mercury and which crystallizes to a pasty mass on cooling and consists of CmHr-CaHsOH. Similar products are obtained from methyl naphthalenes.

What I claim is:

l. The process for the production of non-tertiary alcohols, which comprises acting with an alkylene oxide in the presence of a Friedel-Crafts condensing agent on a hydrocarbon at a temperature up to 100 C.

2. The process for the production of monohydric, non-tertiary alcohols, which comprises acting with an alkylene oxide in the presence of an anhydrous aluminum halide on a hydrocarbon at a temperature up to 100 C.

3. The process for the production of monohydric, non-tertiary alcohols, which comprises acting with an alkylene oxide in the presence of a Friedel-Crafts condensing agent on a hydrocarbon in the liquefied state, at a temperature up to 100' c,

4. The process for the production of monohydric, non-tertiary alcohols, which comprises acting with an alkylene oxide in the presence of an anhydrous aluminum halide on a hydrocarbon ilii,o liquefied state, at a temperature up to C.

5. The process for the production of mono-- hydric, non-tertiary alcohols which comprises acting with an alkylene oxide. in the presence of anhydrous aluminum chloride on a hydrocarbon in the liquefied state, at a temperature u t 100 C.

8.-The process for the production of mono- The lower layer is 7. The process for the production of monohydric, non-tertiary alcohols, which comprises acting with an alkylene oxide in the presence of anhydrous aluminum chloride on a liquid aromatic hydrocarbon at superatmospheric pressure and at a temperature up to 100 C.

8. The process for the production of phenylethyl alcohol, which comprises acting with ethylene oxide in the presence of an anhydrous aluminum halide on benzene at about 5 C.

9. The process for the production of phenylethyl alcohol, which comprises acting with ethylene oxide in the presence of anhydrous aluminum chloride on benzene at about 5' C.

10. A process for the manufacture of aromatic alcohols which comprises reacting ethylene oxide with an aromatic hydrocarbon in the presence of an acid condensing agent and maintaining the temperature of the reaction mass at about 6 C. during substantially the entire reaction period.

11. A process for the manufacture of phenyl propyl alcohol which comprises reacting propylene oxide with benzene in the presence of an acid condensing agent, and maintaining the temperature of the reaction mass below 40 C. during substantially the entire reaction period.

12. A pmcess for the manufacture of phenyl propyl alcohol which comprises reacting propylene oxide with benzene in the presence of anhydrous aluminum chloride, and maintaining the temperature-of the reaction massbelow 40 I C. during substantially the entire reaction period.

, 13. A process for the manufacture of tolyl propyl alcohol which comprises reacting propylene oxide with toluene in the presence of an acid condensing agent, and maintaining the temperature of the reaction mass below 40 C. during substantially the entire reaction period.

14. A process for the manufacture of tolyl propyl alcohol which comprises reacting propylene oxide with toluene in the presence of anhydrous aluminum chloride, and maintaining the temperature of the reaction mass below 40 C., during substantially the entire reaction period.

15. A process for the manufacture of aromatic alcohols, which comprises reacting an alkylene oxide with an aromatic hydrocarbon in the presence of an acid condensing agent and artificially cooling the reaction mass during substantially the' entire reaction period.

'18. A process for the manufacture of aromatic alcohols. which comprises reacting an alkylene oxide with an aromatic hydrocarbon in the presence of an acid condensing agent and keeping the temperature of the reaction mass below 40.

C. during substantially the entire reaction period. 17. A process for the manufacture of aromatic alcohols, which comprises reacting a'n allrylene hydric, non-tertiary alcohols, which comprises.

acting with an alkylene oxide inthe presence of anhydrous aluminum chloride on an aromatic hydrocarbon in the perature up to C.

liquined stataat a temoxide with an aromatic hydrocarbon in the presence of an acid condensing agent at or below room temperature during substantially the entire reaction period.

18. A process for the manufacture of aromatic alcohols, which comprises reacting an alkylene oxide with an aromatic hydrocarbon in the presence of an acid condensing agent and an inert organic diluent, and keeping thetemperaturc of the reaction mass below 40' C. during substantially the entire reaction period. 4

' EIHIRICH HOH'I'. 

